Herbicidal mixture and process for destroying plant life therewith



United States Patent 3,188,194 HERBICIDAL MIXTURE AND PROCESS FOR DESTROYING PLANT LIFE THEREWETH Francois dOgny, Paris, France, assignor to Pechiney-Cie de Produits Chimiques ct Electrometallnrgiques, Paris, France No Drawing. Filed Nov. 15, 1960, Ser. No. 69,305 Claims priority, application France, Nov. 21, 1959,

810,868, Patent 1,249,883

3 Claims. (Cl. 71-2.5)

This invention relates to means and materials for destroying plant life of a selected nature, and relates more particularly to the activation of known herbicidal agents to accelerate or catalyze the actions thereof.

To the present, known herbicidal agents, including the so-called total herbicides, require considerable time before their action has been completely expended to determine the ultimate efiects thereof. During this prolonged reaction, the process is subject to a number of drawbacks, including the possible dilution or elimination of the herbicidal agents by rain or other atmospheric effects beyond the users control. The long-time span before the efiect can be ascertained also reacts negatively on the user from a psychological standpoint.

As a result, it is an object of this invention to provide a means and method for activation of herbicidal agents to accelerate the action thereof, whereby the plant destruction sought to be secured is obtained in a considerably shorter time, such as within several days and preferably within three to five days, rather than the several weeks heretofore required.

Another object is to provide a means and method for use in combination with herbicidal agents whereby such agents can be made efiective for use in the treatment of plants otherwise normally insensitive to the particular herbicidal agent.

In accordance with the practice of this invention, the desired activation of the herbicide is achieved by the combination of the herbicide with an oxygenated compound of phorphorus having the formula wherein R is selected from the group consisting of hydrogen, an alkyl, aryl, aryl-alkyl, cycloaliphatic or heterocyclic groups, and R and R are selected from the group consisting of alkyl, aryl, aryl-alkyl, cycloaliphatic or heterocyclic groups. In other words, at least two of the groups attached to the oxygens connected by a single bond to the phosphorus group is an organic group, While the other is either an organic group or hydrogen.

Representative of the compounds which may be employed in combination with the herbicides, in accordance with the practice of this invention, are tributyl, tricresyl, tri-isobutyl, and the like phosphates. Representative of the herbicidal agents which may be employed in combination with the oxygenated compound of phosphorus are parachlorophenyl-dimehtyl urea, amin'o-triazol, 2-chloro- 4,6-bis(ethylamino)-S-triazine, the solium salt of alphaalpha-dichloropropionic acid, etc. The foregoing are given by way of illustration and not by way of limitation of the oxygenated compounds of phosphorus and the herbicides, it being understood that other oxygenated.

compounds of phosphorus represented by the above formulation can be combined with other known herbicides in a synergistic reaction to catalyze the herbicide in a manner whereby the plant-destroying eifect of the herbicide is greatly accelerated and whereby the plant-destroying eiiect of the herbicide is expanded to provide a more or less herbicidal action on plants not normally sensitive to such agent.

The oxygenated compound of phosphorus is elTective to catalyze the reaction of the herbicide when combined in any amounts. However, best results are secured when the amount of the oxygenated compound of phosphorus i present in the combination with the herbicide in at least stoichiometric proportions.

In practice at least 5 kg. of oxygenated compound of phosphorus is used per hectare and, preferably about 10 to 40 kg. per hectare; the quantity of herbicidal agent then used depends on the said compound one.

The oxygenated compound of phosphorus and the herbicidal agent may be brought together in any conventional manner. For example, in the event that the herbicide is soluble in the phosphorus compound, the former may be dissolved to provide a solution in the latter. In the event that the one is not soluble in the other, a third component in which both are soluble may be employed, either as a carrier or to bring the compounds together. It is preferred to make use of a system which is capable of dispersion or emulsification in aqueous medium. The thus obtained solution, dispersion, or suspension can be applied directly onto the plant to be killed, as by means of an aerosol spray or the like. The phosphorus compound may also be added, after it has eventually been made emulsifiable, to an aqueous slurry which contains one or more herbicidal agents, the latter of which may either be dissolved or else present in the form of an emulsion or suspension in the slurry.

Further, this invention has for another of its objects a new composition of matter comprising a herbicide containing at least one oxygenated compound of phosphorus, as previously described.

The following examples are given by way of illustration but not by way of limitation of the practice of this invention.

EXAMPLE 1 In a hothouse maintained at about 21 C., plantlets of mustard (M), corn (B), and n-asturtium (C) were treated with tributyl phosphate and with tri-isobutyl phosphate as one control, based upon the use of oxygenated compounds of phosphorus alone. Other plants were treated with parachlorophenyl-dimethyl urea and aminotriazol, as another control, based upon use of herbicide alone. Still further. plantlets were treated with a mixture of the above oxygenated compounds of phosphorus and herbicides in accordance with the practice of this invention. Evaluation of the results was made after three days, and again after thirty days, and the determinations are set forth in the following table, in which the numeral Table I Treated plants Used Used products quantities, Results within Results within kgJhectare 3 days 30 days M B C M B C Parachlorophenyldimethyl urea 2 O 0 100 100 95 Aminotriazol 2 0 0 95 80 Tri-isobutyl phosphate t +Emulsifier 2 30 10 70 30 Tri-butyl phsophato 10 +Emulsifier 1.5 30 50 Parachlorophenyl-dimethyl urea- 2 +Tri-isobutyl phosphate 10 100 so 100 100 95 +Emulsifier 2 Parachlorophenyl-dimethyl urea- 2 I +Tri-butyl phosphate 10 100 s0 100 100 98 +Emu1sifier 1. 5

Aminotrlazol 2 +Tri-butyl 10 80 80 100 The emulsifying agent for the phosphates was a condensation product of oleic acid and ethylene oxide.

EXAMPLE 2 Table II----Continued Tests identical to those described in Example 1 were 30 Treated plants carried out n the presence of the following herbicidal U d Se agents (1) 2 chloro bls(ethyl,ammo)s F P Used products quantities, Results within the sodlum salt of alpha-alpha-dichloroproplonlc acid, leg/hectare 5 da s (3) aminotriazol, and (4) sodium chlorate. r

Obtained results are brought together in Table II. M B C Amiri oltrigzol i il fi 1 ri uty p osp ate 10 75 85 Table H +En1ulsifier 1. 5

0 Sodium chlorate +Tributyl phosphate Treated plants +Emulsifier Used u :1 r 11 Used products quantities, Results within means hme lie/hectare 5 days 45 It should be noted, particularly in the case of the SOdllll'll salt of alpha-alpha-dichloropropionic acid, that this her- B C bicide agent, which is used as a selective antigraminacese agent, becomes effective when combined with an oxygen- 2-chlol'o-4frbls(ethY1amm)'S'tT1ame- 5 0 0 0 ated compound of phosphorus, as a herbicide to destroy Sodium salt of alpha-alpha-dichloro- 50 such plants as mustard and nasturtium, plants which were p p 5 0 0 0 heretofore relatively unaffected by the particular com- Amjnotriazol 1 5 0 0 pound when used alone.

Sodium chlorate 2o *1.b Lb. l.b. EXAMPLE 3 Triyl p sp a 10 Various 1 n wer tr e i +Emulsmer L5 100 40 6o 55 p a ts e eated in th field with tr butyl I or tr1cresyl phosphate as representative of the oxygenated g -M- y w- 2 5 compounds of phosphorus and with parachlorophenylf;;g;f f ;ig gggggj' "'5 ""gg dimethyl urea and sodium chlorate, as representative of +Emu1sifler herbicidal agents and with various combinations of the sodium salt ogilpha alpha dichloro 5 60 oxygenated compounds of phosphorus and herbicidal propiomc aci I +Tributy1 phosphate 10 100 75 70 agents The results are set forth 1n the following Table +Emulsifier 1. 5 HI Table III U 6 Results within 5 days Results within 1 month S8 5 Used products quantities,

kgJha. Treated plants Rate of Treated plants Rate of mortality mortality (1) (1) Tributyl phosphate 20 graminaceae 0 graminaceae 0. +Emulsifier 3 horsetails 0 horsetails.-- 0.

(check) 10 planteins" 0 0 min 0. goose-grass 0 g0ose-grass- 0. carrots 0 carrots 0. erigerons 10 erigerons 10.

potentiilas s routs.

See footnotes at end of table.

Table III-Continued U a Results within 5 days Results within 1 month se Used products quantities,

kg./ha. Treated plants Rate of Treated plants Rate 01 mortality mortality Tributyl phos hate 0 graminaceae 0. +Emulsi er 0 horsetail 0.

(check) 0 resp'r. sl. ett I V respr. 0

'Iributyl phosphate 0 10.

+Emu1sifier 0 0;

(check) 50.

0 very sl. att.+ 0 respr. 0 0 0. potentilles. s1. att.

plantains" 0. v sorrels sprouts.

(2) graminaceae 0 graminaceae 0. h0rsetai1s 0 buttercups- 50 respr. buttercups. 0 goose-grass- 100. goose-grass 0 nts.-. sl. att.

' fs 0 coltsfoot. 40. coltsfoot..- 0 plantains 0. potentillas .0 ox eye daisies 0. plantains 0 sorrels sprouts. ox eye daisies 0 r (1) 1) Parachlorophenyl- 2 grammaceae 0 graminaceae 20+respr.

dimethyl urea. horsetails 0 horsetails 70.

(check) cow-parsnips 0 tles 0 ts... 0 artemises 0 graminaceae. 0 graminaceae +respr. horseteils- 0 horsetails.-. 75. mints 0 ts 10. artemises 0 v 1) (1) Sodium chlorate 4O grammaceae 50 graminaceae ($1. respr.)

(check) goose-grass 20 goose/grass 100.

mints "mint 100, sorrels 40- sorrels 50. dandelions 10 dande1ions respr. V compel-Snips" 20 cow-parsnips. 20-1-51. respr. horsetails 10 horsetails..- 10. I

buttercups sprouts.

graminaeeae graminaceae 20 (respr.) mints 20 30.

50 50+sl. respr. potentillas. 50+sl. respr.

Sprouts.

Parachloroplienyldi- 2 graminaceae 95 methyl urea. mints 100 0. +Tributyl phosphate- 20 plantains 100 +Emulsifler--- 3 butteroups 100 0. l

sorrels 7 9O (s1. respr.) goose-grass 100 100. thistles 100 potentillas 100 graminaceae mints 80 100 100 horsetalls 50 Sodium chlorate 40 grammaceae- 50 +Trlbuty1 phosphate- 20 potentiilas- 100 +Emulsifier 3 mints--- 90 thist1es. 100 horsetails 80 2) 2) gremmaceae- 50 grammaceae- 65. potentillas 100 potentillas 100. min 90 mints 100. thistles 90 thistles 100. horseta 90 horsetails 100.

buttercups sl. respr.

See footnotes at end of table.

Table IllContinued Results within days Used Results within 1 month Used products quantities,

kgJha. Rate of v Treated plants mortality Treated plants Rate of mortality Parachlorophenyldlmethyl urea.

+Tricresyl phosphate +Emulslfier gramlnaceae horsetail thlstles sorrels mints graminaceae- In the table, the meaning of the various abbreviations is the following:

ha.(hectare) is 10,000 square meters.

sl.slight.

att.-attack.

respr.resprout.

It will be apparent from the results obtained in Example 1, Table I, that no noticeable elfect is secured from the herbicides when used alone after three days of application, and that negligible results are secured by the use of oxygenated compound of phosphorusseparate and apart from the herbicide. Yet, when both are combined in a single composition and applied onto the plantlets, mortality after three days is almost as great as the mortality secured after thirty days by the herbicide without the phosphate.

The results secured in Example 3 with the various field plants equally demonstrates the lack of effectiveness of the separate components when used alone after five to eightdays of application, and the marked increase to almost complete mortality in the sameflength of time when the same herbicide is applied in combination with the same oxygenated compounds of phosphorus in accordance with the practice of this invention. It should be also noted that the effectiveness of the herbicide is spread to many more plants which are otherwise not effectively treated by the herbicide when used alone.

It will be understood that various changes may be made in the method of formulations and applications without departing from the spirit of the invention, especially as defined in the following claims.

I claim: r

1. A herbicidal composition comprising the combination in admixture of a herbicide selected from the group consisting of parachlorophenyl dimethyl urea, aminotriazol, 2-chloro-4,6-bis(ethyl amino)S-triazine and the sodium salt of alpha-alpha-dichloropropionic acid and an oxygenated compound of phosphorus selected from the group consisting of tributyl phosphate, triisobutyl phosphate and tricresyl phosphate in which the oxygenated compound of phosphorus is present in the combination in at least stoichiometric proportion in the herbicide and and in which the two components are present in herbicidal elfective amounts, and in which the combination is applied in an amount of at least 5 kg. of the oxygenated compound per hectare of plant life.

3. The process as claimed in claim 2 in which the composition is applied in an amount of 10 to 40 kg. per hectare of plant life.

References Cited in the file of this patent UNITED STATES PATENTS Bridgeman Jan. 1, 1952 OTHER REFERENCES Thompson et al. in Botanical Gazette, vol. 107, 1946, pages 475 to 507.

Metcalf: Advances in Pest Control Researc vol. 1, 1957, pages 39 to 79.

Ennis et al. in Science, vol. 103, No. '2677, page 476, April 19, 1946.

Hitchcock et al. in "Contrib. Boyce Thompson -Institute, vol. 15, No. 4, pages 173 to 193, 1948.

Gast et al. in Agricultural Chemicals, vol. 11, No. 4, April 1956, pages 42 to 45, 136 and 137.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,188,194 June 8, 1965 Francois d'Ogny It is hereby certified that error appears in the above numbered patent reqiiring correction and that the said Letters Patent should read as correctedbelow.

Columns 5 and 6, Table III-Continued, in the heading to columns 3 and 4, for "Results within 5 day read Results within 8 days Signed and sealed this 26th day of Octoberj 1965.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Allcsting Officer Commissioner of Patents 

1. A HERBICIDAL COMPOSITION COMPRISING THE COMBINATION IN ADMIXTURE OF A HERBICIDE SELECTED FROM THE GROUP CONSISTING OF PARACHLOROPHENYL DIMETHYL UREA, AMINOTRIAZOL, 2-CHLORO-4,6-BIS(ETHYL AMINO)S-TRIAZINE AND THE SODIUM SALT OF ALPHA-ALPHA-DICHLOROPROPIONIC ACID AND AN OXYGENATED COMPOUND OF PHOSPHORUS SELECTED FROM THE GROUP CONSISTING OF TRIBUTYL PHOISPHATE, TRIISOBUTYL PHOSPHATE AND TRICRESYL PHOSPHATE IN WHICH THE OXYGENATION COMPOUND OF PHOSPHORUS IS PRESENT IN THE COMBINATION IN AT LEAST STOICHIOMETRIC PROPORTION IN THE HERBICIDE AND IN WHICH TWO COMPONENTS ARE PRESENT IN HERBICIDAL EFFECTIVE AMOUNTS. 